USOO5317083A

United States Patent (19) (11) Patent Number: 5,317,083

Freitag et al. (45) Date of Patent: May 31, 1994
(54) PROCESS FOR ISOLATING 58 Field of Search ........................ 528/499, 502, 196
POLYCARBONATES FROM THEIR
SOLUTIONS WITH TUBE HAVING CROSS (56) References Cited
SECTIONAL CONTRICTIONS U.S. PATENT DOCUMENTS
75) Inventors: Dieter Freitag; Claus Wulff; 4,568,418 2/1986 Walko et al. ........................ 528/499
Wolfgang Alewelt; Hermann Kauth, Primary Examiner-Harold D. Anderson
all of Krefeld, Fed. Rep. of Germany Attorney, Agent, or Firm-Connolly & Hutz
73) Assignee: Bayer Aktiengesellschaft, 57 ABSTRACT
Leverkusen, Fed. Rep. of Germany
(21) Appl. No.: 87,908 The present invention relates to a process for isolating
polycarbonates in which a solution of polycarbonate in
(22 Filed: Jul. 9, 1993 an organic solvent is dispersed with steam and which is
(30) Foreign Application Priority Data characterized in that the resulting suspension of poly
carbonate particles, condensed water and water/sol
Jul. 21, 1992 (DE) Fed. Rep. of Germany ....... 4224025 vent vapor is subsequently dried in a tube with cross
51) Int. Cl............................................... C08G 64/40 sectional constrictions.
52 U.S. C. .................................... 528/499; 528/196;
528/.502 6 Claims, 1 Drawing Sheet
U.S. Patent May 31, 1994 5,317,083

d)

o O F1 F2
O() is
F2 f
F2=F1 (0.4 to 0.8)

b)
 1.
5,317,083
2
droxyphenyl)-diisopropyl benzenes and nucleus
PROCESS FOR SOLATING POLYCARBONATES alkylated and nucleus-halogenated compounds thereof.
FROM THEIR SOLUTIONS WITH TUBE HAVING Preferred diphenols are, for example, 4,4'-dihydroxy
CROSS SECTIONAL CONTRICTIONS diphenyl, 2,2-bis-(4-hydroxyphenyl)-propane, 2,4-bis
(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxy
This invention relates to a process for isolating ther phenyl)cyclohexane, a,a'-bis-(4-hydroxyphenyl)-p-
moplastic aromatic polycarbonates from their solutions diisopropylbenzene, 2,2-bis-(3-methyl-4-hydroxy
in which a solution of thermoplastic aromatic polycar phenyl)-propane, 2,2-bis-(3-chloro-4-hydroxyphenyl)-
bonate in an organic solvent is dispersed with steam and propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-methane,
which is characterized in that the resulting suspension O 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, bis
of polycarbonate particles, condensed water and wa (3,5-dimethyl-4-hydroxyphenyl)-sulfone, 2,4-bis-(3,5-
ter/solvent vapor is subsequently dried in a tube with dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-bis
cross-sectional constrictions. (3,5-dimethyl-4-hydroxyphenyl)-cyclohexane, a,a'-bis
The polycarbonate particles thus obtained are distin (3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene
guished by the fact that residual solvent can be better 15 and 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane,
removed. 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane and
The isolation of polycarbonates from their solutions 1,1-bis-4-hydroxyphenyl)-3,3-dimethyl-5-methyl cy
with steam is known perse. cloheane.
Thus, U.S. Pat. No. 3,508,339 describes the use of a Preferred diphenols are, for example, 2,2-bis-(4-
special nozzle in combination with a mixing chamber, in hydroxyphenyl)-propane, 2,2-bis-(3,5-dimethyl-4-
which polycarbonate solution and steam are combined, hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-
and an adjoining tube of constant diameter in which the hydroxyphenyl)propane, 2,2-bis-(3,5-dibrono-4-
solvent is removed by drying. hydroxyphenyl)-propane, 1,1-bis-(4-hydroxyphenyl)-
U.S. Pat. No. 4,212,967 (=EP 3996) claims a combi cyclohexane and 1,1-bis-(4-hydroxyphenyl)-3,3-dimeth
nation of a nozzle of the De Laval type with a heated 25 yl-5-methyl cyclohexane.
tube which increases in diameter from the nozzle. These diphenols are either known from the literature
U.S. Pat. No. 4,568,418 claims a combination of a or may be produced by methods known from the litera
nozzle and an adjoining agglomeration tube, the tube ture. The same applies to the thermoplastic aromatic
being characterized by a constant diameter and by at polycarbonates obtainable therefrom.
least six semicircular loops.
30 The aromatic polycarbonates may be branched by
These known processes give polycarbonate particles incorporation of small quantities, preferably 0.05 to 2.0
which are substantially freed from the organic solvent. mol-% (based on diphenols used), of trifunctional or
However, subsequent drying is necessary to achieve more than trifunctional compounds, for example those
containing three or more than three phenolic hydroxyl
very low residual solvent contents. The necessary con 35 groups.
ditions, for example the necessary time and the directly These polycarbonates are also known from the litera
time-dependent apparatus volume, play an important ture or may be obtained by methods known from the
part in determining the suitability of the isolation pro literature.
cess for application on an industrial scale. Some of the compounds containing three or more
The polycarbonate particles obtained by hitherto 40 than three phenolic hydroxy groups which may be used
known processes are still not entirely satisfactory in in accordance with the invention are, for example,
regard to their subsequent dryability. phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxy
It has now surprisingly been found that the polycar phenyl)-hept-2-ene, 4,6-dimethyl-2,4,6-tri-(4-hydroxy
bonate particles obtained in the isolation of thermoplas phenyl)-heptane 1,3,5-tri-(4-hydroxyphenyl)-benzene,
tic aromatic polycarbonates from their solutions with 45 1,1,1-tri-(4-hydroxyphenyl)-ethane, tri-(4-hydroxy
steam can be freed particularly effectively from residual phenyl)-phenyl methane, 2,2-bis-(4,4-bis-(4-hydroxy
solvent when the polycarbonate solution and the steam phenyl)-cyclohexyl)-propane, 2,4-bis-(4-hydroxy
are combined, for example in a two-component nozzle, phenylisopropyl)-phenol, 2,6-bis-(2-hydroxy-5'-methyl
and the polycarbonate particles formed, which are pres benzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-
ent as a suspension in condensed water and water/sol 50 dihydroxyphenyl)-propane, hexa-4-(4-hydroxy
vent vapor, are further freed from solvent in a tube phenylisopropyl)phenyl-orthoterephthalic acid ester,
directly adjoining the point at which they are com tetra-(4-hydroxyphenyl)-methane, tetra-4-(4-hydroxy
bined, the tube having several cross-sectional constric phenylisopropyl)-phenoxymethane and 1,4-bis-(4,4'-
tions and widening to its original diameter after each dihydroxytriphenyl)-methylbenzene. Some of the
constriction. 55 other trifunctional compounds are 2,4-dihydroxyben
The polycarbonate particles are separated from the zoic acid, trimesic acid, cyanuric chloride and 3,3-bis
vapor phase, for example in a cyclone, and are then (4-hydroxy-3-methylphenyl)-2-oxo-2,3-dihydroindole.
freed from residual solvent in a subsequent drying step. The thermoplastic aromatic polycarbonates in ques
Thermoplastic aromatic polycarbonates which may tion generally have weight average molecular weights
be used in the process according to the invention are the Mw of 10,000 to more than 200,000 and preferably
known aromatic homopolycarbonates, copolycarbon 20,000 to 80,000, as determined by measurement of the
ates and mixtures of these polycarbonates which are relative viscosity in CH2Cl2 at 25 C. and at a concen
derived from the following diphenols: hydroquinone, tration of 0.5g in 100 ml CH2Cl2. Solutions of thermo
resorcinol, dihydroxydiphenylene, bis-(hydroxy plastic aromatic polycarbonates in organic solvents
phenyl)-alkanes, bis-(hydroxyphenyl)-cycloalkanes, bis 65 mainly accumulate where thermoplastic aromatic poly
(hydroxyphenyl)-sulfides, bis-(hydroxyphenyl)-ethers, carbonates are produced by the known interfacial pro
bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)-sul cess or by the process in homogeneous solution, the
fones, bis-(hydroxyphenyl)-sulfoxides, a,a'-bis-(hy so-called pyridine process.
 3
5,317,083
4.
Using these methods, a polycarbonate solution may reducing the radius of the tube. In example 2, the con
be produced, for example, as follows: striction is obtained by the transition from a circular
In a suitable apparatus, 61.2 kg/h of a solution of cross-section to an elliptical cross-section.
48.75 kg 2,2-bis-(4-hydroxyphenyl)-propane, 237 kg
water, 39.4 kg 45% sodium hydroxide, 50 g sodium EXAMPLES
borohydride and 750 p-tert-butyl phenol are continu Example 1
ously phosgenated with 4.75 kg/h phosgene in 90 kg
methylene chloride with addition of 3 kg/h 45% so 7.5 kg bisphenol A polycarbonate having an average
dium hydroxide. molecular weight Mwof 29,800 are dissolved in 42.5 kg
After addition of 40 g/h triethyl amine and 0.75 kg/h 10 methylene chloride. 16 kg/h of this 15% polycarbonate
45% sodium hydroxide, a polycarbonate having a rela solution are combined with 8 kg/h steam (15 bar =200'
tive viscosity of 1.303 is obtained after an average resi C.) in a Tee (internal diameter 4 mm). The third arm of
dence time of half an hour. the Tee is connected to a 100 cm long straight tube with
After separation of the aqueous phase, the organic an internal diameter of 4 mm. The cross-section of the
polycarbonate solution is used for further processing 15 tube decreases from 20 cm to 3 mm over a length of 30
after suitable dilution or concentration. mm. The polycarbonate particles issuing from the end
The solutions of thermoplastic aromatic polycarbon of the tube are separated from water and solvent vapor
ates in the organic solvents have concentrations of 3% in a cyclone.
by weight to 25% by weight and preferably 5% by The particles are dried in vacuo at 120° C. and the
weight to 20% by weight. 20
residual methylene chloride content is determined. The
Suitable solvents apart from the CH2Cl2 already men results are set out in Table 1.
tioned are any solvents which sufficiently dissolve the
polycarbonates and which have a boiling point of not EXAMPLE 2
more than 150 C. Preferred solvents are methylene
chloride, monochlorobenzene, toluene and mixtures of 25 thePolycarbonate solution and steam are combined in
same way as in Example 1 except that the straight
the solvents mentioned.
The steam used has a temperature of 100 C. to 300 tube is replaced by a spiral tube of the same length and
C. and preferably 140 C. to 250 C. the same cross-section. The diameter of the spirals is 60
The ratio of polycarbonate solution to steam is 0.5:1 mm. The tube constrictions correspond to those of Ex
to 6:1 and preferably 1:1 to 5:1. 30 ample 1 in number and dimensions. The results are set
The tube adjoining the point where the polycarbon out in Table 1.
ate solution and the steam are combined has at least
three cross-sectional constrictions in which its cross EXAMPLE 3
sectional area is reduced to 40%-80% of the original Polycarbonate solutions and steam are combined in
area. The constriction extends over a length of at least 35 the same way as in Example 1 except that the straight
3 D, D standing for the original tube diameter, and is tube is replaced by five 10 cm long tube sections con
not sudden, but rather continuous to avoid blockages. nected by semicircular bends (diameter D = 60 mm).
After the constriction, the tube widens to its original The cross-sectional constrictions correspond to those of
cross-section. Example 1 and are situated in the straight sections. The
The length of the tube is at least 50 D where D is as results are set out in Table 1.
defined above.
The tube may be, for example, straight or spiral or COMPARISON EXAMPLE 1
may consist of straight tube sections connected by Polycarbonate solution and steam are combined in
bends of any shape. In one preferred embodiment, the the same way as in Example 1 except that the straight
tube is heated to a temperature 10 C. to 40 C. below 45 tube with cross-sectional constrictions is replaced by a
the glass transition temperature of the polycarbonate to straight tube with no constrictions. The results are set
be isolated.
out in Table 1.
By virtue of their extremely low residual solvent
content, the polycarbonates isolated by the process COMPARISON EXAMPLE 2
according to the invention can be processed by known 50 Polycarbonate solution and steam are combined in
methods to various molded articles, including for exam the same way as in Example 2 except that the spiral tube
ple films, sheets and wires. Typical additives, stabilizers with
against UV light, heat and moisture, mold release tube cross-sectional constrictions is replaced by a spiral
with no constrictions. The results are set out in
agents, dyes, pigments or fillers, such as carbon black, Table 1.
or glass fibers may be added to the polycarbonates iso 55
lated by the process according to the invention before COMPARISON EXAMPLE 3
or during their processing.
The polycarbonate moldings obtained are used for Polycarbonate solution and steam are combined in
typical applications, for example in electrical engineer the same way as in Example 3, except that a tube with
ing, in the optical field, in vehicle construction and in 60 no cross-sectional constrictions is used. The results are
the lighting industry. set out in Table 1.
The accompanying drawings show two examples of COMPARISON EXAMPLE 4
suitable tubes.
FIG. a shows a continuous cross-sectional constric Polycarbonate solution and steam are combined in
tion in a section along the tube. 65 the same way as in Comparison Example 1, except that
FIG. b is a plan view perpendicularly of the tube axis the 100 cm long tube with no constructions is replaced
of two different possibilities for the cross-sectional con by a 10 cm long tube. The results are set out in Table 1.
striction. In example 1, the constriction is obtained by
 5,317,083
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TABLE 1 pension in a tube with cross-sectional constrictions, and
isolating the polycarbonate after drying.
Results of drying at 120 C/30 mbar 2. The process of claim 1, wherein the tube is config
Example 2 3 C1 C2 C3 C. ured such that, in the constricted cross-sectional por
Residual methylene 40 25 30 40 20 20 25 5 tions, the cross-sectional area of the tube is reduced by
chloride after 40 to 80%.
2 hours 3. The process of claim 2, wherein the tube is config
Residual methylene <2 <2 <2 15 15 20 10 ured such that the length of the constricted portion is at
chloride after least three times greater than the tube diameter, and the
6 hours O overall length of the tube is at least 50 times greater than
All values for residual methylene chloride in ppm the tube diameter.
4. The process of claim 1, wherein the tube is a
We claim: straight tube.
1. A process for isolating aromatic thermoplastic 5. The process of claim 1, wherein the tube is a spiral
tube.
polycarbonates from solutions thereof in organic sol 6. The process of claim 1, wherein the tube is heated
vent, comprising dispersing the solution with steam to to a temperature of 10 to 40 C. below the glass transi
form a suspension of polycarbonate particles, con tion temperature of the polycarbonate being isolated.
densed water and water/solvent vapor, drying the sus
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